New azo dyestuffs and their application



Patented Sept. 1, 1931 rarest FFICE RAINALD BRIGHTMAN AN D PERCY CHORLEY, 9F BLACKLEY, MANCHESTER, ENGLAND, ASSIGNORS 'TO BRITISH DYESTUFFS CORPORATION LIMITED, OF MANCHESTER, ENGLAND NEW AZO DYESTUFFS AND THEIR APPLICATION No Drawing. Application filed April 16, 1928, Serial No. 270,572, and in Great Britain April 22, 1927.

According to this invention we obtain new and valuable azo dyestuffs by combining a tetrazotized 4E:4-diamino diphenyl monodior tri-sulphide with two molecules of suitable end components of which at least one is or contains an amino naphthol sulphonic acid including in this term the N-substituted derivatives thereof, directly coupled with the diamino diphenyl sulphide residue. The other coupling component may be any of the known coupling components and either coupling component may contain an azo group. These dyestuiis are represented by the general formula wherein R represents a coupling component, R represents a coupled amino naphthol sulphonic acid and w is an mterger greater than tn SiOaH wherein R represents hydrogen, an acyl group or an aryl group. Either or both of the coupling components can be selected from amino naphthol sulphonic acids of the above type. By the term aryl group I mean a benzene or naphthalene residue which may be further substituted. This relatively unessential partof the molecule can be varied widely without substantially alteringthe important properties of'our compounds.

The 4 F-diamino diphenyl sulphides used by us are crystalline substances of known structure and possess melting points given in the literature, viz., 4:4-diamino diphenyl sulphide, in. p. 108109 C. (Kehrmann and Bauer, Berichte, 1896, 29, 2362) 4: 4-diamino diphenyl disulphide, m. p. 78 C. (Schmidt, Berichte, 1878, 11, 1172) and 4: 4- diamino diphenyl trisulphide, m. p. 122 C. (Hodgson, J. Chem. Soc. 1925, 127, 4.43). 5 They are not the same compounds as the socalled thio-bases obtained by the action of sulphur on aromatic amines, but have diflferent melting points and other properties. The following examples illustrate the invention 100 According to the components used and to the conditions of coupling, we obtain dyestufl's which are valuable for dyeing animal or vegetable fibres or for dyeing regenerated cellulose silks. Certain of the dyestuiiswe obtain give dyeings on wool which are fast to milling and some have the property of giving even dyeings on regenerated cellulose silks. Particularly valuable products are obtained when the 4:4l-diamino diphenyl sulphide is combined with at least one molecule of 2-amino-8-naphthol-6-sulphonic acid or an N substituted derivative thereof. 1

Our advantageous dyes include those formed by tetrazotizing a 4:4J-diamino diphenyl'mono-, dior tri-sulphide and coupling with an amino-naphthol sulphonic acid of the'type OH OH NHz 0 and less than l.

These dyestuffs may be also prepared by another method than the method of the present application indicated above; namely by the method set forth in the application of one of us, Rainald Brightman, Ser. N 0. 262,048. In that application there is disclosed a process which comprises combining a diazotized 411lt1'0l='-L1111I10 diphenyl sulphide with salicylic acid, reducing the nitro group of the resultant dyestuil' by means of sodium sulphide, diazotizing the amino body thus obtained and combining it with an aminonaphthol sulphonic acid. The dyestufi's produced by such a method are of the same general type as herein disclosed.

The present invention is directed to the processes of making these dyestuffs in which a tetrazotized l: F-diamino-diphenyl monodior tri-sulphide is combined with one molecular proportion of an amino-naphthol sulphonic acid including in this term the N- substituted derivatives thereof, and one molecular proportion ofany coupling component.

' phenyl sulphide aretetrazoti zed with .138.

" 630 parts without limiting it, the parts being by weight.

Ewample 1.216 parts of &: y-diamino diphenyl sulphide are dissolved in water and 500 parts of 36 per cent hydrochloric acid. The solution is stirred and cooled with ice and tetrazotized by the gradual addition of 138 parts of sodium nitrite. The tetrazo solution thus obtainedis run into a well-stirred cold'solution of 322 parts of the sodium salt of 1-amino8-naphthol-4-sulphonic acid containing 400 parts otsoda ash. Themixture is stirred and maintained cold until coupling is-completew-hen-it is heated up and'the dyestuff isolated by the addition of common salt. It fonmsa dark powder which is-soluble in sulphuric acid to Prussian blue colored solutions, and: in water to violet solutions. It dyes viscose silk areddish-violet shade, and wool a violet shade.-

Ewam-ple 2.-216.parts of i 4-diamino diphenyl sulphide are tetrazotized with 138 parts of sodium nitrite and 500 parts 053% per cent hydrochloric acid and the tetrazo solution is allowed to run into a solution of of Q-phenyl amino-5-naphthol-7- sul'phonic acid containing 400 parts of sodium carbon-ate. After stirring until coupling is complete, the mixture isheated up and the dyestufi'"isolated by the addition of common salt. It forms a darkpowder, which is soluble in sulphuric acid to navy blue colored solutions, and in water to red solutions. It

dyes viscose silk in bluish-red shades.

Emample 3-216 parts of 4 4-diamino diparts of sodium nitrite and 500 parts of 36 per cent hydrochloric acidaud. the solution of tetrazo comp ound-is stirred into a solutioir containing 138 parts of salicylic acid, 40 parts. of. sodium hydroxide andAOO-partsot so chum.

carbonate. The mixture is stirred until cou pling is complete when a solution of 337 parts of the sodium salt of Q-phenylamino-8-naphg thol-6sulphonic acid is added. Stirring is continued until combination is complete, whenthe mixture is heated up and the dyestutf isolated by the addition of co mon salt.

It forms a dark powder which issoluble in sulphuric acid to violet-blue colored solutions, and in water to brown solut1ons, and

which. dyes viscose silk a brown shade and wool in brown shades. fast to milling. The dye is lClGIltlCill. with the dyestuft prepared from 4t-nitroe4qmino diphenyl sulphide as described. in Example 5 of our co-pending application Serial No. 262,048. If in place of, the 2eplienyl amino-8-naphthol-6-sulphonic acid inthe above example, we use a solution of 239parts of 2-amino-8-naphthol-6- sulphonic acid, we obtain adyestufi' giving red-browndyeingson viscose silk.

Example .To a solution of138parts of salicylic acid in 40 parts of sodium hydroxide and 400 parts of sodium carbonate there is.

coupling is complete when there is added a neutral solution of the amino-azo compound obtained by combining 138 parts of diazo tized of p-nitroaniline with 319 parts of 1- amino-8-naphthol-3z6-disulplionic acid in mineral-acid solution inthe known way. The mixture is maintained alkaline andv stirred until coupling is complete when it is heated up and the dyestuii isolated by the addition of common salt. It forms: a dark lustrous powder which is soluble in sulphuric acid to dull violet-grey colored solutions, and in Water togreen solutions, and which dyes viscosesilk a dark green shade. If in place of 216 parts oi 1:4-diaminodiphenyl sulphide there are used 280 parts of LHF-diamino-diphenyl,trisulphide, we-obtain a dyestufi' givingbright bluish-green shades on viscose silk.

Example -5.280 parts of 4s: F-diamino diphenyl trisulphide are tetrazotized in the presence of ice with 138 parts of sodium nitrite anl 500 parts of 36 per cent hydrochloric acid. The tetrazo-compound. partly separates and the yellow suspension is run into a solution of 138 parts of salicylic acid in 40 parts of sodium hydroxide and 400 parts of sodium, carbonate. until coupling is complete there is added a neutral. solution on 239 partsof 2-amino-5- naphtholr7-sulphonic acid. The mixture is stirred until coupling is complete when it is heated up and the dyestuii precipitated by the-addition of common salt. It forms a reddish-brown powder which is soluble in sulphuric acid to violet colored solutions; in water to orange-red solutions. It dies viscose silk an orange shade.

Ema-mph 6.216 parts of: tzJ-diamino diphenyl sulphide are tetrazotized and combined with138 parts of salicylic acid in alkaline (sodium carbonate) solution.- After stirring about half an hour a. solution con-- taining 315 parts of 2-phenylamino-5-naphthol-T-sulphonic acid is added and the mixture maintained alkaline and stirred. until coupling iscoinplete. It is then heated up After stirring d lot) 254 parts of l: y-sulphophenyl-3-methyl-5- pyrazolone. I After stirring for half an hour a solution of 239 parts of 2-amino-8-naphthol-6-sulphonic acid and 500 parts of sodium carbonate is added and stirring continued until coupling is complete. The mixture is then heated up and the dyestuff isolated by theaddition of common salt. It forms a black powder, giving a navy blue colored solution in concentrated sulphuric acid, turning crimson red on dilution and aifording ultimately a reddish-brown precipitate. It is soluble in water to a brown colored solution which is substantially unchanged on addition of alkali and aifords a reddish precipitate on addition of mineral acids. It dyes viscose silk a yellowish-brown and wool a brown shade, fast to milling.

Example S.-216 parts of l 4-diainiiio diphenyl sulphide are tetrazotized in the usual way and to the solution is added, while stirring, a neutral solution of 239 parts of 2-a1nino-8-naphthol-6-sulphonic acid. After coupling for about one hour, the acid mixture is made alkaline by the addition of 500 parts of sodium carbonate and a solution of 315 parts of Q-phenyl amino-8-naphthol-6- sulphonic acid is run in. Stirring is continued until coupling is complete when the mixture, is heated up and the dyestuff isolated by the addition of common salt. It forms a greyish powder giving a deep blue colored solution in concentrated sulphuric acid turning to violet on dilution and affording ultimately J a violet-brown precipitate. It is soluble in water to a reddish-brown colored solution substantially unchanged on addition of alkali and yielding a violet-brown precipitate on addition of mineral acids. It dies viscose silk a magentaand wool a maroon shade, fast to milling.

Example 9-216 parts of lz y-diamino diphenyl sulphide are tetrazoti'z'ed in the usual way and to the solution of tetrazo compound is added'a solution of 4:7 8 parts of 2-amino-8- naphthol-G-sulphonic acid and 450 parts of sodium acetate crystals. The mixture is stirred untilcoupling is complete, when it is made alkaline, heated up and the dyestufi isolated by the addition of common salt. It forms a black powder soluble in concentrated sulphuric acid giving a navy blue colored solution which turns violet and ultimately yields a bluish red precipitate on dilution. it is soluble in water to reddish blue colored solutions, substantially unchanged on addition of alkali and yielding a bluish red precipitate on addition of mineral acids. It dyes viscose silk a violet-brown and wool a maroon shade, fast to milling. I

Ea2ample 10.2-80 parts of lz lf-diamino diphenyl trisulphide are tetrazotized in the usual way with 138 parts of sodium nitrite. To the suspension of tetrazo compound there is added with stirring a neutral solution containing 478 parts of 2-amino-8naphthol-6- sulphonic acid. Stirring is continued until coupling is complete, when the mixture is made alkaline, heated up and the dyestuff is isolated by the addition of common salt. The dyestufi is a greyish-black powder soluble in concentrated sulphuric acid giving a blue c olour which turns violet and ultimately yields a red-brown precipitate on dilution. It is soluble in water to brownish-red solutions, substantially unchanged on addition of alkali and yielding a red-brown precipitate on addition of mineral acids. It dyes viscose silk a maroon shade'and wool a bordeaux shade, fast to milling.

The following table illustrates further the range of shades obtainable by varying the components Diamine First coupling component Second coupling component shade g 4:4-diamino-diphenyl 2-amino-5-naplithol-7-sulphonie acid 2-amino-5-nanhthol-7-sulphonic acid Scarlet. monosulphide. 4

Do 2-acetamino-8-naphtho1-6-sulphonic aeid 2-acetamino-8-naphthol-G-sulphomc acid.. Bluish-red.

2-amino-5-naphtho1-7-sulphonic acid 2-1)enzoylamino-S-naplitliol-6-siilphon1c ac1d Do. 1-(2:5-dicliloro-4-su1phophcnyl)-3-methyl Z-phenylaminO-Snaplithol-G-sulphonic acid. Yellowish-brown.

-5-pyrazolone (acid coupled). I l-phenplg-methyl-apyrazolone (acid 2-am1no-5naphtholJ-sulphomc acid Scarlet.

coup e l-( y-sulphcplienyl)-3-metl1y1-5-pyrazolone. 2-aminpganaphthol-o-sulphonm acid (acid Orange-red.

coup c 2-phenylamino-8-naphtliol-6-sulplionie acid Brown. 2-acetamino-8-naphthol-G-sulphonic acid Scarlet. 2 amino-8-naphthol-6-su1plicnic acid (acid Do.

coupled) 2-aniino-s-naphthol fi-sulphonie acid 2 if-din ttirophenyl-amino)-8 napthol-6 sul- Reddish-brown.

, p onic aci iz i iliarnino diphenyl dido 2-amino-8 naphthol-6-su1ph0nic acid Violet'brown.

st. phide.

Do 2-amino-5-naphtliol-7-sulphonic acid 2-amino-5-naptho1-7-sulphonic acid. Scarlet. 4:4-diamino-diphcnyl .do o Do.

tri-sulphide.

Do Salicylic acid 2-amino-8'naphtholt-sulphonic acid (alkaline). Reddish-orown.

do 2-acetamino-S-naphthol-fi-sulphonic acid Yellowish-red. do 2-m-xylylamino-S-naplithol-fi-sulphonic acid. Brown.

l-phcnylt-g-methyl-fi-pyr 0 (acid S-hydroxy-2-naphthylglycine-(i-sulphonic acid. Light brown.

coup e l-(4isulpho plienyl)-3-methyl-5-pyra- 2-amino-8-naphtho1-6-sulp1ionic acid l. Yellow.

zo one. izi ldilalrpiino-diphenyl 1-phenyl-3-methyl-5-pyrazolone 8-hydroxy-2-naphthylglycine-G-sulphonic acid. Brown.

st 1) i c.

What We claimand desire to secure lay-Let ters Patent is 1. Theprocess for'the manufacture of; new: azo dyeswhi-ch COIDPIlSGStGtIZlZOiElZlIlg: a d1 amineofthe formulav and coupling the tetrazo compound so produced with twomolecular proportions of an amino naphthol sulphonic acid;

2. New azo dyes having the probable gen,- eral formula wherein a: is an integer greater than and less than 4 and R represents an amino naphthol sulphonic acid, the said dyes being soluble in concentrated sulphuric acid and in water and dyeing viscose silk.

3. New 2120 dyes-having the probable gens e-ral formula 3 wherein R represents an aminonaphthol sulphonic acid, the said dyes being soluble in concentratedsulphuric acid and in water and dyeing viscose silk;

4:. In the manufacture of new azo dyes, the up process which comprises diezotizing a diamine of the formula so n- NHR NHRa HO3S- I OH,

R wherein R represents hydrogen, an: acyl group, or a monocyclic aryl group.

5. Inthe manufacture otnew azo dyes, the process which comprises diazotizing adiamine ofthe formula and coupling the tetrazo compoundsoproe duced with one molecular proportion of 2 6 am1no-5-naphthol-'(-sulphon1c acid and one molecularproportion. of: n a i on p sulphonic; acid of the type wherein R represents hydrogen, an acyl group, or-a monooyclie aryl' group,

6. Newazo dyes having the probable general iormula wherein m is an integer: greater than 0 and less the-n.4, R represents a: coupledrQ-aminm 5i-naphthol-Tsulphonic acid and R represents a coupled aminonaphthol sulphonic acid of the type wherein R represents hydrogen, an acyl group, or amonocyclic aryl group.

7. New azo dyes having the probable gen eral formula NHR:

wherein R. representsacoupled 2-amino-5 naphthol+(-sulphonic acid andRg represents a coupled amino naphthol sulphonicacid'of the type wherein R represents hydrogen, an acyl group or inonocyclic aryl group, the said dyes being soluble in concentrated sulphuric acid andin water and'dyeing viscose silk in even level shades.

8. New azo dyes having the probable general formula wherein R represents a coupled 2-aminos5- naphtholeZ-sulphonic acid and R represents a coupled amino naphthol sulphonic acid of the type wherein R represents. hydrogen,, an acyl group or a monocychc aryl group, said dyes being soluble in concentratedsulphuric 210161 and in water and dyeing viscose silk in even level shades.

9. New azo dyes having the probable general formula wherein R, represents a coupled 2-amino-5- naphthol-7-sulphonic acid, the amino group of which may be represented by the structure -NHR, wherein R represents hydrogen, an acyl group or a monocyclic aryl group.

10. New azo dyes having the probable general formula Nam NHRQ and no.s

wherein R represents hydrogen, an acyl group or a monocyclic aryl group.

11. New azo dyes having the probable general formula wherein R and R are coupled amino naphthol sulphonic acids selected from a group consisting of the structures H03 NHR NHR: and

wherein R represents hydrogen, an acyl group or a monocyclic aryl group.

12. New azo dyes having the probable general formula wherein m is an integer greater than 0 and less than 4 and R represents a coupled 2-amino-8-naphthol-6-sulphonic acid, the amino group of which may be represented by the structure -NHR, wherein R represents hydrogen, an acyl group or a monocyclic aryl group.

13. New azo dyes having the probable general formula wherein R represents a coupled 2-amino-8- naphthol-6-sulphonic acid, the amino group of whlch may be represented by the structure -NHR, wherein R represents hydrogen, an acyl group or a monocyclic aryl group.

14. New azo dyes having the probable general formula wherein m is an integer greater than 0 and less than 4 and R represents a coupled 1- amino-8-naphthol-4-sulphonic acid.

15. New azo dyes having the probable general formula wherein R represents a coupled 1-amino-8- naphthol-4-sulphonic acid.

In testimony whereof we affix our signatures.

RAINALD BRIGHTMAN. PERCY CHORLEY.

OH NH:

soin

(|)H NH: 

